CN117920104A - Continuous production device and continuous production process of perfluoropolyether - Google Patents
Continuous production device and continuous production process of perfluoropolyether Download PDFInfo
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- CN117920104A CN117920104A CN202311766671.4A CN202311766671A CN117920104A CN 117920104 A CN117920104 A CN 117920104A CN 202311766671 A CN202311766671 A CN 202311766671A CN 117920104 A CN117920104 A CN 117920104A
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 41
- 238000010924 continuous production Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 20
- 239000002826 coolant Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000005057 refrigeration Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims description 4
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims 1
- 239000012595 freezing medium Substances 0.000 abstract description 7
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Abstract
The invention relates to the technical field of fluorine-containing fine chemical industry, in particular to a continuous production device and a continuous production process of perfluoropolyether. The production device comprises: the device comprises a tower reactor, a material collecting tank, an evaporator and a condenser; the reaction liquid outlet of the tower reactor is connected with the first inlet of the material collecting tank, and the tail gas outlet of the tower reactor is connected with the third inlet of the condenser; the first outlet of the material collecting tank is connected with the second inlet of the evaporator, the second outlet of the evaporator is connected with the third inlet of the condenser, and the fourth outlet of the condenser is connected with the solvent inlet of the tower reactor. The invention can ensure the continuous production (including post-treatment) of the perfluoropolyether by optimizing the production device, effectively improves the use efficiency of the freezing medium, and has easy control of the reaction process and simple operation.
Description
Technical Field
The invention relates to the technical field of fluorine-containing fine chemical industry, in particular to a continuous production device and a continuous production process of perfluoropolyether.
Background
The perfluoropolyether (PerfluoroPolyethers, abbreviated as PFPEs) is a relatively special high-molecular perfluoropolyether, only has C, F, O elements in the molecule, is colorless, odorless and transparent oily liquid at normal temperature, and is only dissolved in a perfluorinated organic solvent.
PFPEs has the characteristics of heat resistance, oxidation resistance, radiation resistance, corrosion resistance, low volatilization, incombustibility and the like, and has good comprehensive properties of being compatible with plastics, elastomers, metal materials and the like, thereby becoming a lubricant (such as a lubricant used as a component of aerospace machinery and the like) which is extremely reliable in severe environments, and being widely applied to fields of chemical industry, electronics, electricity, machinery, magnetic media, nuclear industry, aerospace and the like.
Fluorine-containing olefin is taken as a raw material, and is subjected to ultraviolet irradiation together with oxygen at low temperature, and oxidation polymerization is carried out to obtain polyether with slightly different structures:
T-O-[CF(CF3)CF2O]m-(CF2O)n-(CF2CF2O)p-(O)q-T＇
Wherein: t, T' = -CF 3、-COF、-CF2-COF、-CF(CF3), -COF, etc., which may be the same or different; n is not equal to 0, q is not equal to 0; p=0 is pure HFP polymerization product; m=0 is pure TFE polymerization product; when p is not equal to 0 and m is not equal to 0, the polymer is mixed polymer of HFP and TFE, and various groups are arranged randomly on the main chain. In a large number of documents and patents, the reaction of tetrafluoroethylene, hexafluoropropylene and oxygen is carried out in a reactor in a batch reaction, the reaction time is short, the efficiency is low, and the solvent is evaporated after the reaction is finished to obtain the perfluoropolyether product. For example, the following patent descriptions:
Patent US3715378 discloses that in a 600cc cylindrical glass reactor, a mixture of tetrafluoroethylene and oxygen in a fluorine-containing solvent at low temperature-80 ℃ is irradiated with ultraviolet lamp to prepare perfluoropolyether, and then the end-COF is treated at high temperature in KOH aqueous solution to obtain perfluoropolyether with end groups-OCF 3 and-OCHF 2, which can have molecular weights of 1500-5000. Patent US4451646 uses tetrafluoroethylene and oxygen as raw materials, and prepares amorphous high-viscosity high-molecular perfluoropolyether with repeating unit-CF 2O-, -CF 2O-greater than 200 and product peroxide value of 4.15wt% in a 600cc cylindrical glass reactor in a fluorine-containing solvent such as CF2Cl2 at-80 ℃ to 35 ℃ under 330nm ultraviolet light irradiation. In US2006/0205982Al is described a 30L cylindrical reactor starting from tetrafluoroethylene and oxygen at a temperature of-80 to-40℃to produce a perfluoropolyether peroxide product in the form of one or a mixture of HFC125/HFC227/FC 218. The molecular weight of the prepared product reaches 35000-45000, and the peroxide value exceeds 1.2%. Patent US5783789 describes the oxidation of tetrafluoroethylene to perfluoropolyether peroxide in a cylindrical reactor at-80 to-50 ℃ in pentafluoroethane under irradiation of ultraviolet lamps and with a high peroxide number of 1 to 3.5wt%.
It can be seen that in the prior art, the photo-oxidation reactors are all batch reaction devices, the device capacity is small, and continuous reaction cannot be realized. After each reaction, the materials and the solvent are required to be discharged, and the materials and the solvent are separated, so that the process is complex and is not beneficial to large-scale production and preparation.
In view of this, the present invention has been made.
Disclosure of Invention
The preparation of perfluoropolyether by using photocatalytic polymerization requires that ultra-low temperature is maintained under ultraviolet irradiation, otherwise explosion risks exist, and a large amount of freezing medium such as liquid nitrogen is consumed for maintaining the ultra-low temperature, so that in view of safety risks and large consumption of the freezing medium, the operation and maintenance are difficult, the degree of industrial production is rarely achieved at home and abroad at present, and production devices and production capacity are generally low.
The invention discovers that the continuous production (including post-treatment) of the perfluoropolyether can be ensured by optimizing the production device, the use efficiency of the freezing medium is effectively improved, the reaction process is easy to control, and the operation is simple.
Based on the above, the specific technical scheme of the invention is as follows:
The invention firstly provides a continuous production device of perfluoropolyether, which comprises the following components: the device comprises a tower reactor, a material collecting tank, an evaporator and a condenser;
The tower bottom of the tower reactor is provided with a raw material gas inlet and a reaction liquid outlet, and the tower top is provided with a solvent inlet and a tail gas outlet; the tower reactor is internally provided with an ultraviolet lamp tube, a filler column plate and filler; a refrigeration jacket is arranged outside the tower reactor, and comprises a cooling medium first feed port and a cooling medium first discharge port;
The material collection tank comprises a first inlet and a first outlet; a refrigerating jacket is arranged outside the material collecting tank and comprises a cooling medium second feeding port and a cooling medium second discharging port;
The evaporator comprises a second inlet, a second outlet and a third outlet;
The condenser comprises a third inlet, a fourth outlet and a fifth outlet;
The connection mode of the device comprises the following steps: the reaction liquid outlet of the tower reactor is connected with the first inlet of the material collecting tank, and the tail gas outlet of the tower reactor is connected with the third inlet of the condenser; the first outlet of the material collecting tank is connected with the second inlet of the evaporator, the second outlet of the evaporator is connected with the third inlet of the condenser, and the fourth outlet of the condenser is connected with the solvent inlet of the tower reactor.
In the invention, the raw material gas inlet at the bottom of the tower reactor is used for continuously introducing oxygen and fluorine-containing olefin, and when the method is implemented, the method can be used for selectively introducing the oxygen and the fluorine-containing olefin through two inlets, or can be used for selectively mixing the fluorine-containing olefin and the oxygen outside the reactor and then introducing the mixture from one inlet, and the method is not limited; the third outlet of the evaporator is used for discharging the reaction product perfluoropolyether.
In the present invention, the inlet and the outlet are provided with valves, such as needle valves, and the like, which are not limited herein.
Preferably, the tower reactor can be a packed tower, the tower body of the tower reactor consists of tower sections, and the number of the tower sections is 1-3 sections; the height can be freely adjusted, so that the reaction conditions, such as molecular weight control, can be well adjusted. Each section is typically selected at 1m, but is not limited thereto.
More preferably, the tower body of the tower reactor is made of stainless steel.
Preferably, the material of the filler column plate and the material of the filler are transparent fluorine-containing plastics, and the material can well prevent the corrosion of materials in the reaction.
More preferably, the material of the filler tower plate and the material of the filler are the same or different, and are fusible polytetrafluoroethylene resin or polyperfluoroethylene propylene resin.
Preferably, the diameter ratio of the packing to the tower reactor is 1: (6-10); for example a packed column using DN200, the packing diameter being 25mm.
In the invention, the diameter of the tower reactor can be adjusted according to the requirement, and the tower diameter is not too small for conveniently installing the ultraviolet lamp, and the inner diameter of the tower reactor is preferably larger than 100mm; more preferably, the nominal diameter of the tower reactor is DN 200-DN 300mm.
Preferably, 2-3 ultraviolet lamps are arranged in each meter of the tower body of the tower reactor, and the wavelength range of the ultraviolet lamps is 200-380 nm; more preferably, the concentration of the wavelength around 360nm is better, and the power is in the range of 10-1000W.
In the present invention, the filler may be processed into various types according to the distribution of the reaction gas in the reactor, such as: pall rings, raschig rings, stepped rings, etc.
In the invention, when the multi-section tower sections of the packed tower are arranged in series, the freezing medium inlet and outlet pipelines can be arranged in series or in parallel. The freezing medium in the freezing jacket flows through to ensure that the solvent in the tower is maintained in a low-temperature state (-60 to minus 20 ℃), and simultaneously, the heat released in the reaction is taken away.
In the invention, the main function of the material collecting tank is to collect solvent and material, and the material collecting tank has a certain buffering function on reaction products so as to ensure that the reaction products are not disturbed by the reaction gases, thereby the reaction products can well settle and be collected at the bottom of the tank. The material collection tank is also provided with a refrigeration jacket to keep the solvent and material at a low temperature, preferably below-30 ℃.
In a specific implementation, when the liquid level in the tower reactor reaches a certain height, a certain amount of reaction liquid materials are indicated and collected at the bottom of the material collection tank, and at the moment, a valve at the first outlet at the bottom is opened to discharge the reaction liquid materials into the evaporator.
Preferably, the valve at the first outlet can be designed as an automatic discharging valve controlled by liquid level interlocking, so that manual operation can be further reduced, and industrial continuity degree is provided.
In the present invention, the evaporator is used to distill a small amount of solvent (usually 1-20% of the solvent in the collected material) from the reaction solution material at room temperature, wherein the solvent evaporates out and enters the condenser to return to the reactor. Meanwhile, the reaction gas is discharged from the top of the tower reactor, and the solvent carried out by the condensation and reflux of the reaction gas is condensed through a top condenser.
The invention further provides a continuous production process of perfluoropolyether, which adopts the continuous production device of perfluoropolyether, and the preparation process comprises the following steps:
filling a fluorine-containing solvent in the tower reactor, continuously introducing oxygen and perfluoroolefin at the bottom of the tower reactor, dispersing the gas through the solvent in the tower, and reacting at-60 to-20 ℃ under the radiation of an ultraviolet lamp; collecting the perfluoropolyether product generated by the reaction in the material collecting tank, and after the liquid level in the tank reaches a certain height, allowing the perfluoropolyether product to enter the evaporator; and evaporating the fluorine-containing solvent in the evaporator into the condenser at room temperature, and cooling and returning to the tower reactor.
Preferably, the density of the solvent is less than 1.7g/ml; more preferably, the solvent density is 1.1 to 1.5g/ml; for example, heptafluoropropane has a density of 1.41g/ml, difluorochloromethane has a density of 1.41g/ml, and pentafluoroethane has a density of 1.24g/ml.
Preferably, the perfluoroolefin includes one or more of tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and hexafluoropropylene.
Based on the technical scheme, the invention has the beneficial effects that:
the invention can ensure the continuous production (including post-treatment) of the perfluoropolyether by optimizing the production device, effectively improves the use efficiency of the freezing medium, and has easy control of the reaction process and simple operation.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a continuous production apparatus for perfluoropolyether provided in example 1 of the present invention; wherein the figure is drawn with an "x" representing the filler, and reference numeral 7 in the reference numeral;
Reference numerals: the device comprises a tower reactor 1, a material collecting tank 2, an evaporator 3, a condenser 4, an ultraviolet lamp tube 5, a filler column plate 6, a filler 7, a refrigeration jacket 8, a raw material gas inlet 9, a reaction liquid outlet 10, a solvent inlet 11, a tail gas outlet 12, a first inlet 13, a first outlet 14, a second inlet 15, a second outlet 16, a third outlet 17, a third inlet 18, a fourth outlet 19, a fifth outlet 20, a cooling medium first feed inlet 21, a cooling medium first discharge outlet 22, a cooling medium second feed inlet 23 and a cooling medium second discharge outlet 24.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, all of the starting materials used in the examples were commercially available conventional starting materials, and the technical means used were conventional means well known to those skilled in the art.
The molecular weight of the perfluoropolyether in the following examples was analyzed by liquid chromatography and the peroxide value was measured by the starch potassium iodide method.
Example 1
This embodiment first provides a continuous production apparatus (see fig. 1) of perfluoropolyether, comprising: a tower reactor 1, a material collecting tank 2, an evaporator 3 and a condenser 4;
Wherein, the tower reactor 1 is internally provided with an ultraviolet lamp tube 5, a filler tower plate 6 and a filler 7; a refrigeration jacket 8 is arranged outside the tower reactor 1, and the refrigeration jacket 8 comprises a cooling medium first feed port 21 and a cooling medium first discharge port 22; the tower bottom of the tower reactor 1 is provided with a raw material gas inlet 9 and a reaction liquid outlet 10, and the tower top is provided with a solvent inlet 11 and a tail gas outlet 12; the material collection tank 2 comprises a first inlet 13 and a first outlet 14 (material collection tank reaction liquid outlet); a freezing jacket 8 is arranged outside the material collection tank 2, and the freezing jacket 8 comprises a cooling medium second feed port 23 and a cooling medium second discharge port 24; the evaporator 3 comprises a second inlet 15 (evaporator inlet), a second outlet 16 (evaporator vapor phase solvent outlet) and a third outlet 17 (discharge port); the condenser 4 comprises a third inlet 18 (a condenser gas phase (containing reaction solvent and tail gas) inlet), a fourth outlet 19 (a condenser liquid phase (solvent) reflux inlet) and a fifth outlet 20 (a non-condensable gas outlet (containing reaction tail gas and excessive oxygen)); the "x" portions of the graph represent the filler.
The connection mode of the device comprises the following steps: the reaction liquid outlet 10 of the tower reactor 1 is directly connected with the first inlet 13 of the material collecting tank 2 without a valve; the tail gas outlet 12 of the tower reactor 1 is connected with the third inlet 18 of the condenser 4; the first outlet 14 of the material collection tank 2 is connected with the second inlet 15 of the evaporator 3, the second outlet 16 of the evaporator 3 is connected with the third inlet 18 of the condenser 4, and the fourth outlet 19 of the condenser 4 is connected with the solvent inlet 11 of the tower reactor 1.
The invention further provides a continuous production process of perfluoropolyether by using the continuous production device, which comprises the following steps:
Stainless steel tube DN200 is used as a tower body of the tower reactor 1, the tower body is provided with a freezing jacket 8, the tower body is composed of 1 section of tower section, the length of the tower section is 1 meter, two ultraviolet lamp holes (with built-in power of 120W and ultraviolet lamp 5 with wavelength of 250 nm) are formed in the tower section, a filling tower plate 6 and a filling 7 use poly-perfluoroethylene propylene resin, and the volume of a material collecting tank is 50L. 75L of heptafluoropropane is added into the tower reactor 1 as a reaction solvent, and a liquid level meter displays a liquid level of 1500mm. The material collection tank 2, the tower reactor 1 and the condenser 4 are cooled to-50 to-45 ℃, an ultraviolet lamp 8 is started, mixed gas of 10NL tetrafluoroethylene per minute and 10NL oxygen per minute is continuously introduced from the bottom of the tower reactor, and after 1 hour, a liquid level gauge reaches 1680mm. The first outlet 14 at the bottom of the material collection tank is opened, the material is slowly discharged through the second inlet 15 into the evaporator 3, a small amount of volatile components (about 8-10% of sampling analysis) in the material volatilize in the evaporator 3, enter the condenser 4 through the third inlet 18 from the second outlet 16 of the evaporator 3, and then flow back to the tower reactor 1 through the solvent inlet 11 of the tower reactor 1 from the fourth outlet 19. After the reaction was continued for 24 hours, the volatile component was volatilized from the evaporator to give about 55Kg of a reaction product material, which had an average molecular weight of 1440 as determined by sample analysis liquid chromatography and a peroxy value of 0.09%.
Example 2
The present embodiment provides a continuous production process of perfluoropolyether, which is performed by using the continuous production apparatus in embodiment 1, and the production process includes:
The stainless steel tube of DN200 is used for manufacturing the tower body of the tower reactor 1, the tower body is provided with a freezing jacket 8, the tower body is composed of 3 sections of tower sections, the length of each section of tower section is 1 meter, two ultraviolet lamp holes (the built-in power is 120W, the ultraviolet lamp 5 with the wavelength of 250 nm) are arranged on each section of tower section, the filling tower plate 6 and the filling 7 use the poly-perfluoroethylene propylene resin, and the volume of a collecting tank is 50L. 125L of heptafluoropropane is added into the tower reactor 1 as a reaction solvent, and a liquid level gauge displays a liquid level of 3500mm. The material collection tank 2, the tower reactor 1 and the condenser 4 are cooled to-50 to-45 ℃, the ultraviolet lamp 5 is started, mixed gas of 10NL tetrafluoroethylene per minute and 10NL oxygen per minute is continuously introduced from the bottom of the tower reactor 1, and after 1 hour, the liquid level gauge reaches 3700mm. The first outlet 14 at the bottom of the material collection tank is opened, the material is slowly discharged through the second inlet 15 into the evaporator 3, a small amount of volatile components (about 8-10% of sampling analysis) in the material volatilize in the evaporator 3, enter the condenser 4 through the third inlet 18 from the second outlet 16 of the evaporator 3, and then flow back to the tower reactor 1 through the solvent inlet 11 of the tower reactor 1 from the fourth outlet 19. After the reaction was continued for 24 hours, the volatile component was volatilized from the material in the evaporator 3 to obtain about 74Kg of a reaction product material, and the average molecular weight was 2260 by sampling analysis liquid chromatography, and the peroxy value was 0.28%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A continuous production apparatus for perfluoropolyether, comprising: the device comprises a tower reactor, a material collecting tank, an evaporator and a condenser;
The tower bottom of the tower reactor is provided with a raw material gas inlet and a reaction liquid outlet, and the tower top is provided with a solvent inlet and a tail gas outlet; the tower reactor is internally provided with an ultraviolet lamp tube, a filler column plate and filler; a refrigeration jacket is arranged outside the tower reactor, and comprises a cooling medium first feed port and a cooling medium first discharge port;
The material collection tank comprises a first inlet and a first outlet; a refrigerating jacket is arranged outside the material collecting tank and comprises a cooling medium second feeding port and a cooling medium second discharging port;
The evaporator comprises a second inlet, a second outlet and a third outlet;
The condenser comprises a third inlet, a fourth outlet and a fifth outlet;
The connection mode of the device comprises the following steps: the reaction liquid outlet of the tower reactor is connected with the first inlet of the material collecting tank, and the tail gas outlet of the tower reactor is connected with the third inlet of the condenser; the first outlet of the material collecting tank is connected with the second inlet of the evaporator, the second outlet of the evaporator is connected with the third inlet of the condenser, and the fourth outlet of the condenser is connected with the solvent inlet of the tower reactor.
2. The continuous production apparatus of perfluoropolyether according to claim 1, wherein the material of the filler tray and the material of the filler are the same or different transparent fluoroplastic; preferably, the material of the filler tower plate and the material of the filler are the same or different, and are fusible polytetrafluoroethylene resin or polyperfluoroethylene propylene resin.
3. The continuous production apparatus of perfluoropolyether according to claim 1 or 2, characterized in that the ratio of the filler to the diameter of the tower reactor is 1: (6-10).
4. A continuous production apparatus for perfluoropolyether according to any one of claims 1 to 3, wherein the column body of the column reactor is composed of column sections, the number of which is 1 to 3 sections; preferably, the tower body of the tower reactor is made of stainless steel.
5. The continuous production apparatus of perfluoropolyether according to any one of claims 1 to 4, wherein the inner diameter of the tower reactor is larger than 100mm; preferably, the nominal diameter of the tower reactor is DN 200-DN 300mm.
6. The continuous production apparatus of perfluoropolyether according to any one of claims 1 to 5, wherein 2 to 3 ultraviolet lamps are provided per meter of the tower body of the tower reactor, and the wavelength range of the ultraviolet lamps is 200 to 380nm.
7. A continuous production process of perfluoropolyether, characterized in that it adopts the continuous production apparatus of perfluoropolyether according to any one of claims 1to 6, said preparation process comprising:
filling a fluorine-containing solvent in the tower reactor, continuously introducing oxygen and perfluoroolefin at the bottom of the tower reactor, dispersing the gas through the solvent in the tower, and reacting at-60 to-20 ℃ under the radiation of an ultraviolet lamp; collecting the perfluoropolyether product generated by the reaction in the material collecting tank, and after the liquid level in the tank reaches a certain height, allowing the perfluoropolyether product to enter the evaporator; and evaporating the fluorine-containing solvent in the evaporator into the condenser at room temperature, and cooling and returning to the tower reactor.
8. The continuous process for the production of perfluoropolyether of claim 7, wherein the solvent has a density of less than 1.7g/ml; preferably, the density of the solvent is 1.1 to 1.5g/ml.
9. The continuous production process of perfluoropolyether according to claim 7 or 8, wherein the solvent comprises one or more of heptafluoropropane, difluorochloromethane and pentafluoroethane.
10. The continuous production process of perfluoropolyether according to any one of claims 7 to 9, wherein said perfluoroolefin comprises one or more of tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene and hexafluoropropylene.
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